JP7767971B2 - Dye printing treatment liquid composition, composition set, printing method, and ink-jet printing method - Google Patents

Description

The present invention relates to a dye printing treatment liquid composition, a composition set, a printing method, and an inkjet printing method.

When dyeing fabric with a colorant to produce a printed textile, a technique has been known in which the fabric is pretreated with a treatment liquid to improve the color development and fastness of the colorant. One such technique is disclosed in Patent Document 1, for example, in which a pretreatment liquid made of an aqueous composition is applied to polyester fabric.

JP 2009-249773 A

However, the pretreatment liquid in Patent Document 1 has the problem that it is difficult to obtain printed items with excellent rub fastness, wash fastness, and color development. To begin with, Patent Document 1 is a technology for polyester fabrics, and does not describe printing on natural fiber fabrics. Unlike natural fiber fabrics, polyester fabrics can be printed using dyes without using a pretreatment liquid.

The present invention relates to a treatment liquid composition for dye printing that is applied to fabric and contains a polyester resin, a tertiary amine, an isocyanate group-containing compound serving as a crosslinking agent, and water, wherein the content of the tertiary amine is 1% by mass or more and 5% by mass or less relative to the total amount of the treatment liquid composition.

3 is a flowchart illustrating an example of an indirect textile printing method according to the present embodiment.

The following describes in detail an embodiment of the present invention (hereinafter referred to as the "present embodiment"); however, the present invention is not limited to this embodiment, and various modifications are possible without departing from the spirit of the present invention.

1. Dye Printing Treatment Liquid Composition The dye printing treatment liquid composition of this embodiment (hereinafter also referred to as "treatment liquid composition") is a treatment liquid composition to be applied to a fabric, and contains a polyester resin, a tertiary amine, an isocyanate group-containing compound as a crosslinking agent, and water, wherein the content of the tertiary amine is 1% by mass or more and 5% by mass or less relative to the total amount of the treatment liquid composition. The treatment liquid composition is preferably used to be applied to a fabric before dye printing.

According to this embodiment, the treatment liquid composition is applied to fabric in advance, and then the fabric to which the treatment liquid composition has been applied is dye-printed, thereby obtaining a printed fabric with excellent abrasion fastness, washing fastness, and color development.

Although the reason why such excellent effects are obtained by this embodiment is not clear, the inventors presume as follows.
That is, inks containing disperse dyes or the like typically used in textile printing have low affinity for fabrics containing fibers such as cotton, making dye printing difficult. On the other hand, inks containing disperse dyes or the like easily dye polyester resins due to non-covalent bonds such as hydrogen bonds with carboxy groups, π-π interactions with hydrophobic moieties such as phenyl groups, and van der Waals forces in the polyester resin structure. Furthermore, polyester resins have high affinity for fabrics containing fibers, and therefore can be present on the fabric. Therefore, by attaching polyester resin to fabric using a treatment liquid composition, it is possible to impart the dyeability of inks containing disperse dyes or the like to fabrics containing fibers such as cotton.

However, the polyester resin is only attached to the fabric, not bonded to it. Therefore, due to insufficient adhesion between the polyester resin and the fabric, the resulting printed textile tends to have poor abrasion resistance and washing fastness. In order to improve abrasion resistance and washing fastness, it is conceivable to attach a large amount of polyester resin to the fabric. However, attaching a large amount of polyester resin also results in a large amount of ink being attached, which tends to form an ink-derived coating on the fabric and impair the texture of the printed textile.

On the other hand, the treatment liquid composition of this embodiment contains a polyester resin, an isocyanate group-containing compound as a crosslinking agent, and a specific amount of tertiary amine. Compared to primary amines and secondary amines, tertiary amines can moderately promote the reaction between the isocyanate group-containing compound, polyester resin, and fabric, resulting in binding. This allows for favorable binding between the polyester resin and fabric, making it possible to obtain printed textiles that have excellent friction fastness and washing fastness, as well as a good texture. Furthermore, because polyester resin is easily dyed, it is believed that the printed textiles also have good color development. However, the reason is not limited to this.

Next, we will explain each component contained in the treatment liquid composition, but we will discuss fabrics later.

1.1 Polyester Resin The treatment liquid composition contains a polyester resin.
When the treatment liquid composition contains a polyester resin, it is possible to obtain a printed textile having excellent abrasion fastness, washing fastness, and color development, as well as good texture.

The polyester resin may, for example, have structural units derived from a polycarboxylic acid and structural units derived from a polyhydric alcohol.

Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, succinic anhydride, and p-hydroxybenzoic acid, as well as salts thereof. Examples of salts include potassium salts, sodium salts, calcium salts, and magnesium salts.

Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolethylsulfonate, and potassium dimethylolpropionate.

The polyester resin preferably contains hydroxyl groups, carboxyl groups, sulfonic acid groups, and their sodium salts. The polyester resin may contain one or more of these groups.

The sulfonic acid group-containing polyester resin has, for example, a structural unit derived from a polycarboxylic acid, a structural unit derived from a polyhydric alcohol, and a structural unit derived from a sulfonic acid group-containing aromatic monomer.
Examples of sulfonic acid group-containing aromatic monomers include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 4-sulfo-1,8-naphthalenedicarboxylic anhydride, as well as salts thereof. As for the salts, the above may be referred to, and sodium salts are preferred.

The inclusion of these groups in the polyester resin allows the polyester resin to react well with the isocyanate group-containing compounds described below, improving adhesion to fabrics, preferably fabrics containing fibers with hydroxyl groups. This makes it possible to obtain printed textiles with better texture, as well as superior abrasion fastness, wash fastness, and color development.

In order to produce printed products with excellent texture, as well as excellent abrasion resistance, washing resistance, and color development, it is preferable for the polyester resin to contain hydrophobic moieties such as aromatic groups in its structure.

Polyester resins can be obtained, for example, by selecting one or more of the above-mentioned polycarboxylic acids, polyhydric alcohols, and, if necessary, sulfonic acid group-containing aromatic monomers, and synthesizing them through a conventional polycondensation reaction.

Commercially available polyester resins can also be used. Examples of commercially available polyester resins include Eliteal (registered trademark) KA-5071S, KT-8803, KT-9204, KT-8701, KT-8904, and KT-0507 (all trade names, Unitika Ltd., polyester resin emulsions); Hi-Tec (registered trademark) SN-2002 (trade name, Toho Chemical Industry Co., Ltd., polyester resin emulsion); and Pluscoat (registered trademark). Examples include: Z-221, Z-446, Z-561, Z-565, RZ-570, Z-592, Z-687, Z-690, Z-730, Z-760, RZ-105, RZ-570, and RZ-760 (all trade names, manufactured by GOO Chemical Industry Co., Ltd.); and Vylonal (registered trademark) MD-1200, MD-1500, and MD-2000 (all trade names, manufactured by Toyobo Co., Ltd.).

Polyester resins may be used alone or in combination of two or more types.

In order to obtain a printed textile having even better texture as well as better rub fastness, wash fastness, and color development, the content of the polyester resin is preferably 2% by mass or more and 20% by mass or less, calculated as solids, relative to the total amount of the treatment liquid composition. In order to obtain a printed textile having even better texture as well as better rub fastness, wash fastness, and color development, the content of the polyester resin is more preferably 2% by mass or more and 15% by mass or less, and even more preferably 2% by mass or more and 10% by mass or less, calculated as solids, relative to the total amount of the treatment liquid composition.

Since a printed textile having even better texture, as well as better rub fastness, wash fastness, and color development, can be obtained, the total content of the polyester resin and the isocyanate group-containing compound described below is preferably 3% by mass or more and 23% by mass or less, and more preferably 3% by mass or more and 15% by mass or less, in solids content relative to the total amount of the treatment liquid composition. Since a printed textile having even better texture, as well as better rub fastness, wash fastness, and color development, can be obtained, the total content of the polyester resin and the isocyanate group-containing compound described below is even more preferably 3% by mass or more and 10% by mass or less, in solids content relative to the total amount of the treatment liquid composition.

1.2 Tertiary Amine The treatment liquid composition contains a tertiary amine. The content of the tertiary amine is 1% by mass or more and 5% by mass or less relative to the total amount of the treatment liquid composition.

By using a specific amount of tertiary amine in the treatment liquid composition along with the polyester resin and the isocyanate group-containing compound, it is possible to obtain printed textiles that have excellent abrasion fastness, wash fastness, and color development, as well as a good texture.

The tertiary amine preferably has a hydroxyl group, as this provides the treatment liquid composition with superior storage stability, better abrasion fastness, wash fastness, and color development, as well as a printed textile with a better texture. When a tertiary amine with a hydroxyl group is used, the curing reaction between the polyester resin and the isocyanate group-containing compound in the treatment liquid composition proceeds relatively slowly, which tends to result in the treatment liquid composition having excellent storage stability.

The tertiary amine preferably has a standard boiling point of 340°C or less, since this results in a printed fabric with better texture, as well as better rub fastness, wash fastness, and color development. Using a tertiary amine with a standard boiling point of 340°C or less tends to result in less tertiary amine remaining in the printed fabric, thereby tending to result in even better rub fastness. Because this makes it more difficult for tertiary amine to remain in the printed fabric, even better rub fastness is obtained, and a printed fabric with better texture, as well as better wash fastness and color development, is obtained, the upper limit of the standard boiling point is more preferably 300°C or less, even more preferably 200°C or less, and even more preferably 100°C or less. The lower limit of the standard boiling point is preferably 50°C or more, since this results in a printed fabric with better texture, as well as better rub fastness, wash fastness, and color development. In this specification, standard boiling point means the boiling point at 1 atmosphere.

The tertiary amine is preferably a compound represented by formula (1), since it can provide a printed material having better texture as well as better rub fastness, wash fastness and color development.
R ¹ -N(R ² )-R ³ ...(1)
In formula (1), ^R1 , ^R2 , and ^R3 each independently represent a linear or branched alkyl group having from 1 to 10 carbon atoms, a linear or branched hydroxyalkyl group having from 1 to 10 carbon atoms, or a linear or branched alkoxy group having from 1 to 10 carbon atoms. ^R1 , ^R2 , and ^R3 may have a substituent such as a halogen atom, as long as the effect of the present invention is not impaired.

As a result of obtaining printed textiles with even better texture, along with even better abrasion fastness, washing fastness, and color development, linear or branched alkyl groups having 1 to 10 carbon atoms are preferred, with linear or branched alkyl groups having 1 to 6 carbon atoms being more preferred, and linear or branched alkyl groups having 1 to 4 carbon atoms being more preferred. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-ethylhexyl, n-nonyl, and n-decyl groups.

As a linear or branched hydroxyalkyl group having from 1 to 10 carbon atoms, a linear or branched hydroxyalkyl group having from 1 to 6 carbon atoms is preferred, and a linear or branched hydroxyalkyl group having from 1 to 4 carbon atoms is more preferred, as this results in printed textiles with even better texture, as well as better abrasion fastness, washing fastness, and color development. Such hydroxyalkyl groups include, for example, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, and a hydroxyoctyl group.

As a result of obtaining printed textiles with even better texture, along with even better abrasion fastness, washing fastness, and color development, linear or branched alkoxy groups having 1 to 10 carbon atoms are preferred, with linear or branched alkoxy groups having 1 to 6 carbon atoms being more preferred, and linear or branched alkoxy groups having 1 to 4 carbon atoms being more preferred. Examples of such alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-hexanoxy, and 2-methylpropoxy.

Examples of compounds represented by formula (1) include trialkylamines such as trimethylamine, triethylamine, tri-n-butylamine, diisopropylethylamine, diethyl-n-butylamine, methyldi-n-butylamine, and methylethyl-n-butylamine; N,N-dialkylalkanolamines such as N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dipropylethanolamine, and N,N-dibutylethanolamine; N-alkyldialkanolamines such as N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and N-methyldipropanolamine; and trialkanolamines such as triethanolamine, tripropanolamine, triisopropanolamine, and tributanolamine.

Since this produces printed textiles with even better texture, along with even better abrasion fastness, washing fastness, and color development, the compound represented by formula (1) is preferably one or more selected from the group consisting of trialkylamines and trialkanolamines, and more preferably one or more selected from the group consisting of triethanolamine, triisopropanolamine, and triethylamine.

The compound represented by formula (1) is preferably a trialkylamine, and more preferably triethylamine. These tertiary amines are less likely to remain on the printed material, so using these tertiary amines tends to result in even better rub fastness.

The compound represented by formula (1) is preferably a trialkanolamine, and more preferably one or more selected from the group consisting of triethanolamine and triisopropanolamine. The use of such a tertiary amine makes it possible to more effectively suppress the curing reaction between the polyester resin and the isocyanate group-containing compound in the treatment liquid composition, which tends to further improve the storage stability of the treatment liquid composition.

Tertiary amines may be used alone or in combination of two or more types.

The content of tertiary amine is preferably 1% by mass or more and 3% by mass or less of the total amount of the treatment liquid composition, as this results in printed textiles with better washing fastness, better rubbing fastness, color development, and good texture.

In order to obtain printed textiles with excellent texture as well as superior abrasion fastness, washing fastness, and color development, the mass ratio of tertiary amine to the content of the isocyanate group-containing compound described below is preferably 0.3 to 5, and more preferably 1 to 5.

1.3 Crosslinking Agent The treatment liquid composition contains an isocyanate group-containing compound as a crosslinking agent.
The treatment liquid composition contains an isocyanate group-containing compound together with a specific amount of a tertiary amine, and the isocyanate group-containing compound appropriately crosslinks with the polyester resin and the fabric, enabling the polyester resin and the fabric to be suitably bonded together. As a result, a printed textile can be obtained that has excellent friction fastness, washing fastness, and color development, as well as good texture.

The isocyanate group-containing compound used as the crosslinking agent can be appropriately selected from known crosslinking agents, and may be one that initiates the crosslinking reaction at room temperature or by heat. Examples of such compounds include crosslinking agents with self-crosslinking properties, compounds with multiple functional groups in the molecule that react with unsaturated carboxylic acid components, and metals with polyvalent coordination sites.

Examples of compounds containing isocyanate groups include water-dispersible (blocked) polyisocyanates. Note that (blocked) polyisocyanates refer to polyisocyanates and/or blocked polyisocyanates.

Examples of water-dispersible polyisocyanates include polyisocyanates that have been given hydrophilic properties by polyethylene oxide chains and are dispersed in water using an anionic dispersant or nonionic dispersant.

Examples of polyisocyanates include diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; and derivatives (modified products) of polyisocyanates such as trimethylolpropane adducts, biuret adducts, and isocyanurates of these diisocyanates. The polyisocyanate may also have an isocyanurate skeleton within its structure. These polyisocyanates may be used alone or in combination of two or more.

Water-dispersible blocked polyisocyanates are produced by blocking the isocyanate groups of water-dispersible polyisocyanates with a blocking agent. Examples of blocking agents include diethyl malonate, ethyl acetoacetate, ε-caprolactam, butanone oxime, cyclohexanone oxime, 1,2,4-triazole, dimethyl-1,2,4-triazole, 3,5-dimethylpyrazole, and imidazole. These blocking agents may be used alone or in combination of two or more.

The isocyanate group-containing compound preferably has an isocyanurate skeleton in its structure, and more preferably is a water-dispersible polyisocyanate having an isocyanurate skeleton in its structure. Because isocyanate group-containing compounds with an isocyanurate skeleton have at least three crosslinking points, they tend to be able to better bond the polyester resin to the fabric. This tends to result in printed textiles with better texture, as well as better abrasion fastness, washing fastness, and color development.

Commercially available crosslinking agents containing isocyanate groups can also be used. Examples of commercially available products include Fixer #100ECO, #104EA, #220, 70ECO, #70, #410, and #400 (all trade names, Murayama Chemical Laboratory Co., Ltd.); and Elastron (registered trademark) BN-11, BN-27, BN-69, and BN-77 (all trade names, Dai-ichi Kogyo Seiyaku Co., Ltd.).

The isocyanate group-containing compound may be used alone or in combination with two or more types.

The content of the isocyanate group-containing compound is preferably 1% by mass or more and 3% by mass or less, calculated as solids content, of the total amount of the treatment liquid composition, since this results in printed textiles with better washing fastness, better rubbing fastness, and color development, as well as an even better texture.

1.4. Water The treatment liquid composition contains water.
After the treatment liquid composition is applied to the fabric, the water evaporates and dissipates upon drying. Examples of water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as water from which ionic impurities have been removed as much as possible, such as ultrapure water. Water sterilized by ultraviolet irradiation or the addition of hydrogen peroxide is preferred because it can suppress the growth of mold and bacteria when the treatment liquid composition is stored for a long period of time.

The water content is from 30% to 98% by mass, preferably from 35% to 96% by mass, and more preferably from 40% to 94% by mass, based on the total amount of the treatment liquid composition. By setting the water content within this range, an increase in the viscosity of the treatment liquid can be suppressed, improving the workability when applying the treatment liquid to a fabric and the drying properties after application.
The treatment liquid composition is preferably an aqueous treatment liquid composition, since this provides higher affinity and safety to fabrics, preferably fabrics containing fibers having hydroxyl groups. In this embodiment, "aqueous" refers to a composition in which the water content relative to the total amount of the composition is 30 mass % or more.

1.5. Other Components The treatment liquid composition may contain various additives such as surfactants, solubilizing agents, viscosity adjusters, pH adjusters, antioxidants, preservatives, mildew inhibitors, corrosion inhibitors, and chelating agents.
The additives may be used alone or in combination of two or more.

The content of each additive is, for example, 0.01% by mass or more and 5.0% by mass or less relative to the total amount of the treatment liquid composition.

1.6. Method for Preparing Treatment Liquid Composition The treatment liquid composition can be prepared by mixing the components in any order and, if necessary, performing filtration or the like to remove impurities, foreign matter, etc. The components can be mixed by sequentially adding the components to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, and stirring and mixing the components. Filtration methods include centrifugal filtration and filter filtration.

1.7 Physical Properties of Treatment Liquid Composition The physical properties of the treatment liquid composition can be adjusted as desired depending on the type of fabric and the method of adhering the composition to the fabric, i.e., the application method, etc. The application method of the treatment liquid composition will be described later.

The viscosity of the treatment liquid composition at 20° C. is preferably 1.5 mPa·s or more and 100 mPa·s or less. By setting the viscosity of the treatment liquid within this range, it is possible to improve the coatability, such as the ease with which the treatment liquid spreads when applied to a fabric.
The viscosity of the treatment liquid composition is measured, for example, using a viscoelasticity tester MCR-300 (manufactured by Physica). Specifically, the temperature of the treatment liquid composition is adjusted to 20°C, and the viscosity can be measured by reading the shear viscosity (mPa s) at a shear rate of 200 (1/s).

1.7.2. Surface tension The surface tension of the treatment liquid composition at 25°C is preferably 30 mN/m or more and 50 mN/m or less. By setting the surface tension of the treatment liquid composition at 25°C within this range, the treatment liquid composition exhibits appropriate wettability and permeability to fabrics. Furthermore, since the treatment liquid composition is more easily absorbed uniformly into the fabric, it is possible to suppress differences in the amount of adhesion that occur when the treatment liquid composition is applied, i.e., the occurrence of uneven application.
The surface tension of the treatment liquid composition can be measured, for example, using an automatic surface tensiometer CBVP-Z (Kyowa Interface Science Co., Ltd.) Specifically, the surface tension can be measured by wetting a platinum plate with the treatment liquid composition in an environment of 25°C.

2. Inkjet ink composition The inkjet ink composition (hereinafter also referred to as "ink composition") is used to produce a printed textile by printing on a fabric to which the treatment liquid composition of this embodiment has been applied. Next, the ink composition will be described.
The ink composition according to this embodiment contains a disperse dye and water.

2.1. Disperse Dyes The ink composition contains a disperse dye as a dye because it provides excellent color development to fabrics to which the treatment liquid composition is applied. Disperse dyes are typically particulate colorants that are dispersed in a dispersion medium by a dispersant. Disperse dyes are typically nonionic dyes that have a hydrophilic group and a moderately polar group. Disperse dyes may be used alone or in combination of two or more types.

Examples of disperse dyes include C.I. Disperse Yellow, C.I. Disperse Red, C.I. Disperse Blue, C.I. Disperse Orange, C.I. Disperse Violet, C.I. Disperse Green, C.I. Disperse Brown, and C.I. Disperse Black.

Among them, sublimable dyes are preferred as dispersants. Here, the term "sublimable dye" refers to a dye that has the property of sublimating when heated.
Specific examples of such sublimable dyes include C.I. Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, and 86; C.I. Disperse Orange 1, 1:1, 5, 20, 25, 25:1, 33, 56, and 76; C.I. Disperse Brown 2; C.I. Disperse Red 11, 50, 53, 55, 55:1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190:1, 207, 239, and 240; C.I. Vat Red 41; C.I. Disperse Violet 8, 17, 23, 27, 28, 29, 36, and 57; C.I. Disperse Blue 14, 19, 26, 26:1, 35, 55, 56, 58, 64, 64:1, 72, 72:1, 81, 81:1, 91, 95, 108, 131, 141, 145, and 359; C.I. Solvent Blue 36, 63, 105, and 111.

In this embodiment, cyan dyes, red dyes, and yellow dyes are preferred because they provide better dyeability to the fabric to which the treatment liquid composition is applied, resulting in a printed product with sufficient color development. C.I. Disperse Blue 359 is more preferred as a cyan dye because it provides even better dyeability and a printed product with sufficient color development. C.I. Disperse Red 60 is more preferred as a red dye. C.I. Disperse Yellow 54 is more preferred as a yellow dye.

From the perspective of more effectively and reliably achieving the effects of this embodiment, the content of the colorant is preferably 0.05% by mass or more and 20% by mass or less relative to the total amount of the ink composition.

2.2 Water The ink composition contains water.
As for the water, reference can be made to the water contained in the above-mentioned treatment liquid composition, including the preferred embodiments.

From the perspective of more effectively and reliably achieving the effects of this embodiment, the water content is preferably 30% by mass or more and 80% by mass or less relative to the total amount of the ink composition.

2.3. Dispersant The ink composition may contain a dispersant.
When the ink composition contains a dispersant, the dispersibility of the disperse dye is excellent and the clogging resistance of the ink composition is excellent. Examples of dispersants include sodium naphthalenesulfonate-formalin condensates and resins. The sodium naphthalenesulfonate-formalin condensates are compounds obtained by formalin condensation of a sulfonated compound having a naphthalene ring in the molecule, or salts thereof. The dispersants may be used alone or in combination of two or more.

The dispersant preferably contains a resin, as this provides better dispersibility. Examples of resins include urethane-based resins, styrene-acrylic resins, acrylic resins, fluorene-based resins, polyolefin-based resins, rosin-modified resins, terpene-based resins, polyester-based resins, polyamide-based resins, epoxy-based resins, vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymers, and ethylene-vinyl acetate-based resins. Among these, urethane-based resins and styrene-acrylic resins are preferred, with styrene-acrylic resins being more preferred, due to their excellent clogging resistance.

The urethane resin is not particularly limited as long as it contains a urethane bond in the molecule. Examples of urethane resins include polyether-type urethane resins that contain ether bonds in the main chain in addition to urethane bonds, polyester-type urethane resins that contain ester bonds in the main chain, and polycarbonate-type urethane resins that contain carbonate bonds in the main chain. Urethane resins may be used alone or in combination of two or more types.

Commercially available urethane resins can also be used. Examples of commercially available products include Takelac (registered trademark) W6110 (product name) manufactured by Mitsui Chemicals, Inc., Acrit (registered trademark) WBR-022U (product name) manufactured by Taisei Fine Chemical Co., Ltd., Permarin (registered trademark) UX-368T (product name), Euplen (registered trademark) UXA-307 (product name), and U-Coat (registered trademark) UWS-145 (product name) manufactured by Sanyo Chemical Industries, Ltd., and Solsverse (registered trademark) 47000 (product name) manufactured by The Lubrizol Corporation.

Examples of styrene-acrylic resins include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic ester copolymers, styrene-α-methylstyrene-acrylic acid copolymers, and styrene-α-methylstyrene-acrylic acid-acrylic ester copolymers. These copolymers may be in the form of random copolymers, block copolymers, alternating copolymers, or graft copolymers.

Commercially available styrene-acrylic resins can also be used. Examples of commercially available products include JONCRYL (registered trademark) 67 (product name) manufactured by BASF Japan Ltd. and Solsverse (registered trademark) 43000 (product name) manufactured by The Lubrizol Corporation.

From the perspective of more effectively and reliably achieving the effects of this embodiment, the content of the dispersant is preferably 3.0% by mass or more and 8.0% by mass or less relative to the total amount of the ink composition.

2.4. Surfactant The ink composition may contain a surfactant.
Examples of surfactants include acetylene glycol surfactants, fluorine-based surfactants, and silicone-based surfactants. The surfactants may be used alone or in combination of two or more.

Examples of acetylene glycol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and its alkylene oxide adducts, and 2,4-dimethyl-5-decyne-4-ol and its alkylene oxide adducts.
Commercially available acetylene glycol surfactants may also be used, such as Olfine (registered trademark) 104 series (trade name) and E series (trade name) manufactured by Nissin Chemical Industry Co., Ltd., and Surfynol (registered trademark) series (trade name) manufactured by Air Products and Chemicals Inc.

Examples of fluorine-based surfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkyl amine oxide compounds.
As the fluorine-based surfactant, commercially available products can also be used, such as S-144 (trade name) and S-145 (trade name) manufactured by Asahi Glass Co., Ltd.

Examples of silicone surfactants include polysiloxane compounds and polyether-modified organosiloxanes.
As the silicone surfactant, commercially available products can also be used, such as BYK (registered trademark) series products 306, 307, 333, 341, 345, 346, 347, 348, and 349 (all trade names) manufactured by BYK Japan K.K.

From the perspective of more effectively and reliably achieving the effects of this embodiment, the content of the surfactant is preferably 0.5% by mass or more and 5.0% by mass or less relative to the total amount of the ink composition.

2.5. Water-soluble organic solvent The ink composition may contain a water-soluble organic solvent.
Examples of the water-soluble organic solvent include glycerin; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol monomethyl ether. glycol monoethers such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and methyl triglycol; nitrogen-containing solvents such as 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone; and alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, tert-butanol, isobutanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol.
The water-soluble organic solvents may be used alone or in combination of two or more.

From the perspective of more effectively and reliably achieving the effects of this embodiment, the content of the water-soluble organic solvent is preferably 5% by mass or more and 30% by mass or less relative to the total amount of the ink composition.

2.6 Other Components The ink composition may contain various additives such as a dissolution aid, a viscosity adjuster, a pH adjuster, an antioxidant, a preservative, a mildew inhibitor, a corrosion inhibitor, and a chelating agent for capturing metal ions that affect dispersion.
The additives may be used alone or in combination of two or more.

Preservatives include sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, and 1,2-dibenzinethiazolin-3-one.
Commercially available preservatives can also be used, such as CRL, BND, GXL, XL-2, and TN (all trade names) of the Proxel (registered trademark) series manufactured by Lonza Japan Co., Ltd. One type of preservative may be used alone, or two or more types may be used in combination.

The content of each additive is 0.01% by mass or more and 5.0% by mass or less relative to the total amount of the ink composition.

2.7. Method for Producing Ink Composition The ink composition can be prepared by mixing a disperse dye, water, and, if necessary, other components in any order, and removing impurities and foreign matter, if necessary, by filtration or the like. The components can be mixed by sequentially adding the components to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, and stirring and mixing the components. Examples of filtration methods include centrifugal filtration and filter filtration.

In addition, to better disperse the disperse dye in the ink composition, a dye dispersant may be prepared in advance and used in place of the disperse dye when preparing the ink composition. The dye dispersant can be obtained, for example, by mixing the disperse dye, water, and dispersant in any order and dispersing the mixture using a paint shaker or the like.

3. Composition Set The composition set comprises the treatment liquid composition and the ink composition.

In this embodiment, the treatment liquid composition is first applied to a fabric to obtain a fabric with the treatment liquid composition applied thereto. Then, by printing the fabric with the treatment liquid composition applied thereto using an ink composition, a printed fabric can be obtained that has excellent abrasion fastness, wash fastness, and color development, as well as a good texture.

4. Fabric Examples of fabrics according to this embodiment include natural fibers such as cotton, linen, wool, leather, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, acrylic, and polyurethane; and biodegradable fibers such as polylactic acid. The fabric may also be a blend of these fibers.

The fabric preferably contains fibers having hydroxyl groups, and cotton is more preferred, as this results in printed fabrics with better abrasion fastness, washing fastness, and color development, as well as a good texture. The fibers having hydroxyl groups may also be blends of these fibers.

Examples of the form of fabric include woven fabrics, knitted fabrics, nonwoven fabrics, textiles, as well as clothing and other accessories. Examples of clothing and other accessories include sewn T-shirts, handkerchiefs, scarves, towels, carrier bags, cloth bags, curtains, sheets, bedspreads, wallpaper, and other furniture; and fabrics before and after cutting as parts before sewing. These forms include long rolls, cut to a specified size, and finished products. It is sufficient for the fabric to have the treatment liquid composition adhered to it, and fabrics to which the treatment liquid composition has already been applied may also be used.

The basis weight of the fabric is preferably, for example, 1.0 oz or more and 10.0 oz or less. Good recording can be achieved if the basis weight of the fabric is within this range.

The fabric may be one that has already been colored with a dye. The treatment liquid composition is less likely to leave treatment marks, so it can be used on pre-colored fabrics. In other words, even if the fabric is colored, it is possible to print with minimal treatment marks, thereby improving the quality and commercial value of the printed textile product.

Dyes that can be used to pre-color fabrics include, for example, water-soluble dyes such as acid dyes and basic dyes; disperse dyes used in combination with dispersants; reactive dyes; and solvent dyes. When using cotton fabrics, it is preferable to use disperse dyes and reactive dyes that are suitable for dyeing cotton, with disperse dyes being more preferred.

5. Textile Printing Method The textile printing method of the present embodiment includes a treatment liquid composition application step of applying the treatment liquid composition to fabric.
This step provides a fabric having the treatment liquid composition adhered thereto, and by applying an ink composition to this fabric, a printed textile having excellent rub fastness, wash fastness, and color development, as well as good texture, can be obtained.

The textile printing method preferably includes, after the treatment liquid composition application step, an ink composition application step in which an ink composition is applied to the fabric to which the treatment liquid composition has been applied. The ink composition applied to the fabric is not particularly limited as long as it contains a disperse dye, and for example, the inkjet ink composition according to this embodiment can be used. Furthermore, with regard to the ink composition application step, reference can be made to the textile printing method using the inkjet method described below.
The printing method can be applied to various fabrics and can produce good printing.

The amount of the treatment liquid composition applied to the fabric is, for example, preferably from 0.02 g/ ^cm to 0.5 g/ ^cm , and ^more preferably from 0.02 g/ ^cm to 0.3 g/cm. By setting the amount of the treatment liquid composition applied within the above range, the treatment liquid composition can be applied more uniformly to the fabric, aggregation unevenness in the image on the printed textile can be further suppressed, and color development can be improved.

Examples of methods for adhering the treatment liquid composition to a fabric include a dip coating method in which the fabric is immersed in the treatment liquid composition, a roller coating method in which the treatment liquid composition is applied using a mangle roller, a roll coater, or the like, a spray coating method in which the treatment liquid composition is sprayed using a spray device, or an inkjet coating method in which the treatment liquid composition is sprayed by an inkjet method. Of these coating methods, the treatment liquid composition may be adhered to the fabric using one method alone, or two or more methods may be combined to adhere the treatment liquid composition to the fabric.
In this embodiment, it is preferable to apply the treatment liquid composition to the fabric using a roller such as a mangle roller or a roll coater, because this increases the degree of freedom in designing the amount of treatment liquid composition to be applied, makes it less likely that problems will occur during application, and enables the treatment liquid composition to be applied uniformly to the fabric.

The textile printing method includes a drying step in which the treatment liquid composition applied to the fabric is dried after the treatment liquid composition application step in which the treatment liquid composition applied to the fabric is applied, and it is preferable that the drying temperature in the drying step is equal to or higher than the normal boiling point of the tertiary amine contained in the treatment liquid composition. The treatment liquid composition may be dried by natural drying, but drying accompanied by heating is preferable, as this increases the amount of treatment liquid composition applied to the fabric and also increases the drying speed.

When the drying temperature is equal to or higher than the normal boiling point of the tertiary amine, the tertiary amine is less likely to remain in the printed fabric, which tends to result in a printed fabric with even better rub fastness. The drying temperature is preferably, for example, 300°C or lower, and more preferably 200°C or lower. This prevents the sublimation of the dye caused by heat drying, even if the fabric is pre-colored with a dye, and prevents fading of the fabric color. The lower limit of the heating temperature is sufficient as long as the medium, such as water, contained in the treatment liquid composition volatilizes; for example, it is preferably 50°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher.

Heating methods include, for example, heat press, atmospheric steam, high-pressure steam, and Thermofix. Heat sources include, for example, infrared rays (lamp).

In the textile printing method, after the treatment liquid composition has been applied to the fabric, a washing step may be included as necessary. By including this step in the textile printing method, components contained in the treatment liquid composition that have not adhered to the fabric can be removed.

6. Inkjet Textile Printing Method The inkjet textile printing method is a method in which an ink composition is applied to a fabric to which a treatment liquid composition has been applied using an inkjet method. By employing the inkjet method, dyed portions of fine patterns can be easily and reliably formed. Furthermore, the method can be applied to various fabrics, and good printing can be performed. The inkjet textile printing method can also be used to perform good printing with little color difference between the front and back of thick fabrics. Examples of inkjet textile printing methods include an indirect textile printing method and a direct textile printing method.

6.1. Inkjet Recording Apparatus The inkjet recording apparatus used in the textile printing method is not particularly limited as long as it has at least an ink container containing an ink composition and a recording head connected thereto, and is capable of ejecting the ink composition from the recording head to form an image on a fabric to which the treatment liquid composition has been applied, or on transfer paper as an intermediate transfer medium. Furthermore, either a serial type or a line type inkjet recording apparatus can be used. These types of inkjet recording apparatus are equipped with a recording head, and while changing the relative positional relationship between the fabric or transfer paper and the recording head, droplets of the ink composition are ejected intermittently and in a predetermined volume from the nozzle holes of the recording head at predetermined timing. This allows the ink composition to be applied to the fabric or transfer paper, forming a predetermined transfer image.

Generally, in serial inkjet recording devices, the direction of transport of the recording medium and the direction of reciprocating motion of the recording head intersect, and the relative positional relationship between the recording medium and the recording head is changed by combining the reciprocating motion of the recording head and the recording medium transport motion. In such cases, the recording head generally has multiple nozzle holes arranged, and a row of nozzle holes, or nozzle row, is formed along the recording medium transport direction. Furthermore, the recording head may have multiple nozzle rows formed depending on the type and number of ink compositions.

In general, in line-type inkjet recording devices, the recording head does not reciprocate, but rather changes the relative positional relationship between the recording medium and the recording head by transporting the recording medium. Even in this case, the recording head generally has multiple nozzle holes arranged in a nozzle row that runs in a direction that intersects with the direction of recording medium transport.

6.2. Indirect Printing Recording Method The inkjet printing method of this embodiment includes a treatment liquid composition application step of applying a treatment liquid composition to a fabric, a discharge step of ejecting an ink composition from a recording head and depositing it on an intermediate transfer medium, and a transfer step of transferring the ink composition deposited on the intermediate transfer medium to the fabric to which the treatment liquid composition obtained in the treatment liquid composition application step has been deposited. Specifically, in this printing method, an ink composition containing a disperse dye such as a sublimable dye is ejected from a liquid ejection head, which is a recording head, and deposited on the intermediate transfer medium. The surface of the intermediate transfer medium to which the ink composition has been deposited and the surface of the fabric to which the treatment liquid composition has been deposited are heated while facing each other, thereby transferring the disperse dye contained in the ink composition to the fabric to which the treatment liquid composition has been deposited. In this embodiment, this type of printing method is also referred to as an indirect printing recording method. This printing method can be used to produce good printing regardless of the type of fabric.

6.2.1. Treatment Liquid Composition Applying Step For the treatment liquid composition applying step, reference can be made to the above-mentioned textile printing method.

In the ejection process, the heated ink composition is ejected from the liquid ejection head and adhered to the intermediate transfer medium. Specifically, the pressure generating means is driven to eject the ink composition filled in the pressure generating chamber of the liquid ejection head from the nozzle.

As the intermediate transfer medium, for example, paper such as plain paper, and recording media provided with an ink-receiving layer can be used. The recording media provided with the ink-receiving layer are called, for example, inkjet paper and coated paper. Among these, paper provided with an ink-receiving layer containing inorganic particles such as silica is more preferred. This makes it possible to obtain an intermediate record in which bleeding and other issues are suppressed on the recording surface during the drying process of the ink composition applied to the intermediate transfer medium. Furthermore, such a medium makes it easier to retain the disperse dye on the surface of the recording surface, allowing for more efficient sublimation of the disperse dye in the subsequent transfer process.

In this process, multiple types of ink compositions may be used. This makes it possible, for example, to broaden the color gamut that can be expressed. One of the multiple types of ink compositions may be the ink composition of this embodiment, or two or more may be the ink composition of this embodiment.

The transfer process is a process in which the surface of the intermediate transfer medium on which the ink composition is adhered and the surface of the fabric on which the treatment liquid composition is adhered are heated while facing each other, thereby transferring the disperse dye contained in the ink composition to the fabric on which the treatment liquid composition is adhered. As a result, the disperse dye is transferred, and a printed textile is obtained, which is the fabric on which the ink composition is adhered.

In this process, the intermediate transfer medium to which the ink composition has been applied may be heated while facing the fabric to which the treatment liquid composition has been adhered. In this process, it is more preferable to heat the intermediate transfer medium and the fabric to which the treatment liquid composition has been adhered while they are in close contact with each other. This makes it possible, for example, to record a clearer image on the fabric to which the treatment liquid composition has been adhered, i.e., to dye it.

Heating methods include, for example, steaming with steam, heat pressing with dry heat, thermosol, HT steamer using superheated steam, and HP steamer using pressurized steam. The fabric to which the ink composition has been applied may be subjected to heat treatment immediately, or after a predetermined time has passed. Dry heat is the preferred heating method, as it produces a printed fabric with excellent texture as well as excellent abrasion fastness, washing fastness, and color development.

The heating temperature is preferably 160°C or higher and 220°C or lower, and more preferably 190°C or higher and 210°C or lower. By keeping the heating temperature within this range, the energy required for transfer can be reduced, which tends to improve the productivity of the printed textile. In addition, the color development of the printed textile tends to be better.

The heating time depends on the heating temperature, but is preferably 30 to 120 seconds, and more preferably 40 to 90 seconds. By keeping the heating time within this range, the energy required for transfer can be reduced, which tends to improve the productivity of the printed textile. The color development of the printed textile also tends to be improved.

The amount of ink composition that adheres to the fabric by transfer is preferably, for example, 1.5 mg/ ^cm2 or more and 6.0 mg/ ^cm2 or less per unit area of the fabric. When the amount of ink composition adhered is within the above range, the color development of images, etc. formed by textile printing is improved, and the drying properties of the ink adhered to the fabric are ensured, reducing the occurrence of bleeding of images, etc.

6.2.4 Other Steps The present method may include intermediate processing steps and post-processing steps as necessary.

An example of the intermediate treatment step is a step of preheating the fabric to which the treatment liquid composition has been applied.
An example of the post-treatment step is a step of washing the printed material.

6.2. Direct Printing Recording Method The inkjet printing method may include a treatment liquid composition application step of applying a treatment liquid composition to a fabric, and an ink composition application step of ejecting an ink composition from a recording head and applying the ink composition to the fabric to which the treatment liquid composition obtained in the treatment liquid composition application step has been applied. In this embodiment, this type of printing method is also referred to as a direct printing recording method. This printing method can easily and reliably form dyed portions with fine patterns. Furthermore, because it does not require the use of a plate such as an intermediate transfer medium, it has excellent on-demand properties and can be suitably adapted to small-scale production and multi-item production.

6.2.1. Step of Obtaining Fabric to Which Treatment Liquid Composition Has Been Applied With regard to the treatment liquid composition application step, reference can be made to the above-mentioned textile printing method.

Ink composition application step, an ink composition is applied to the fabric to which the treatment liquid composition has been applied. The ink composition application step may also include a step of applying an additional ink composition onto the area to which the ink composition has been applied.

In the ink composition application step, the maximum amount of ink applied to the fabric is preferably 50 mg/cm2 or ^more and 200 mg/cm2 ^{or less} , and more preferably 80 mg/cm2 ^{or more} and 150 mg/cm2 or ^less . When the maximum amount of ink applied is within the above range, color development is improved. In addition, the image has excellent friction fastness, and aggregation unevenness tends to be less noticeable.

In this process, it is preferable to heat the fabric to which the treatment liquid composition has been applied when the ink composition is applied. This makes it possible, for example, to record a clearer image on the fabric to which the treatment liquid composition has been applied, i.e., to dye it.

Heating methods include, for example, heat press, atmospheric steam, high-pressure steam, and Thermofix. Heat sources for heating include, for example, hot air, infrared rays, and microwaves.

During heating, it is preferable that the surface temperature of the heated fabric be 60°C or higher and 180°C or lower. Having a surface temperature within this range reduces damage to the inkjet head and fabric, and also makes it easier for the ink to spread evenly and penetrate the fabric. The surface temperature can be measured, for example, using a non-contact thermometer (product name "IT2-80", manufactured by Keyence Corporation).

The heating time is preferably, for example, between 5 seconds and 5 minutes. By keeping the heating time within this range, it is possible to sufficiently heat the fabric while reducing damage to the inkjet head and fabric.

6.2.3 Other Steps This method may include intermediate and post-treatment steps as needed. For details of these steps, refer to the other steps in the indirect textile printing and recording method described above.

The present invention will be explained in more detail below using examples and comparative examples. The present invention is not limited in any way by the following examples.

1. Dye printing treatment composition 1.1. Preparation of dye printing treatment composition [Examples 1 to 9 and Comparative Examples 1 to 6]
Each component was placed in a mixing tank so as to have the composition shown in Table 1, mixed and stirred, and then filtered through a 5 μm membrane filter to obtain each treatment liquid composition.

The numerical values for the blend amount of each component in Table 1 represent mass %. The blend amounts of polyester resin and crosslinker represent blend amounts (mass %) calculated as solid content equivalents. "Tg" for polyester resin represents the glass transition temperature (°C). "b.p." for amine represents the standard boiling point (°C) at 1 atmosphere. "Total content of polyester resin and amine" represents the total amount (mass %) of the polyester resin content (mass %) calculated as solid content equivalents and the amine content (mass %) in the treatment liquid composition. "Mass ratio of amine content to crosslinker content" represents the mass ratio of amine content (mass %) to crosslinker content (mass %) calculated as solid content equivalents in the treatment liquid composition.

The components shown in Table 1 are as follows:
(Polyester resin)
KT-8803...Eliteal (registered trademark) KT-8803 (product name, Unitika Ltd., solid content: 30% by mass)

(amine)
Triethanolamine (tertiary amine, normal boiling point: 335°C)
Triethylamine (tertiary amine, normal boiling point: 89.7°C)
Diethanolamine (secondary amine, normal boiling point: 217°C)

(Crosslinking agent)
#220...Fixer #220 (trade name, Murayama Chemical Laboratory Co., Ltd., isocyanate group-containing compound having an isocyanurate skeleton in its structure, solid content: 40% by mass)
WS-500...Epocross (registered trademark) WS-500 (trade name, Nippon Shokubai Co., Ltd., oxazoline group-containing compound, solid content: 39% by mass)

1.2. Evaluation of dye printing treatment liquid composition [Storage stability]
The dye printing treatment compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 6 were left to stand at room temperature for 7 days. Thereafter, each of the treatment compositions obtained was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
A: Separation of solid matter was not observed in the treatment liquid composition.
B: Separation of solid matter was observed in the treatment liquid composition.

2. Preparation of Inkjet Ink Composition [Ink C]
The components were placed in a mixing tank and mixed and stirred for 2 hours using a stirrer to obtain the composition shown in Table 2. The mixture was then filtered through a membrane filter with a pore size of 1 μm to obtain ink C as an ink composition. The numerical values for each component in Table 2 represent mass %.

The components shown in Table 2 are as follows:

(dye dispersant)
Disperse Blue 359: C.I. Disperse Blue 359 (commercially available product)

(Water-soluble organic solvent)
・Propylene glycol ・Glycerin ・Methyl triglycol

(Surfactant)
BYK(R)-348: BYK(R)-348 (trade name, silicone surfactant, manufactured by BYK Japan Co., Ltd.)

3. Preparation of printed textiles 3.1. Preparation of fabrics with treatment liquid compositions attached (Examples 1 to 9 and Comparative Examples 1 to 6)
The treatment liquid composition was adhered to fabric using each of the treatment liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 6. Specifically, fabrics to which the treatment liquid composition was adhered were obtained as follows.
The fabric was prepared by immersing a white cotton blade #4000 (product name, manufactured by Toyobo Co., Ltd.) in the treatment liquid composition, and applying the treatment liquid composition to the fabric with a mangle roller so that the wringing rate was 80%. The fabric was then dried at 140°C for 2 minutes and then further dried at 170°C for 1 minute to obtain fabrics each having the treatment liquid composition adhered thereto.

The drawing ratio (S) was calculated by the following formula (2).
S (%) = [(A-B)/B] x 100...(2)
In the formula (2), S represents the wringing rate (%), A represents the mass of the fabric to which the treatment liquid composition has been applied, and B represents the mass of the fabric before the treatment liquid composition has been applied.

3.2. Preparation of intermediate recording medium with ink composition attached (Examples 1 to 9 and Comparative Examples 1 to 6)
The ink C was filled into the cartridge of an inkjet printer PX-G930 (trade name, manufactured by Seiko Epson Corporation). Then, the ink was applied to the coated surface of coated paper (TRANSJET Sportline 1254 (trade name), manufactured by Chem Paper Co., Ltd.) serving as an intermediate transfer medium, at a resolution of 720 dpi x 720 dpi, with an ink ejection rate of 12 mg/ ^inch² at 100% duty, to form an image having a solid pattern. This yielded an intermediate recording medium with the ink composition applied thereto.

3.3. Textile printing (Examples 1 to 9 and Comparative Examples 1 to 6)
The image-formed surface of the intermediate recording medium having the ink composition adhered thereto obtained above was thermally transferred to each of the fabrics (cotton blades) having the treatment liquid composition adhered thereto using a heat press machine TP-608M (trade name, manufactured by Taiyo Seiki Co., Ltd.) at a temperature of 200°C, a pressure of 4.2 N/ ^cm3 , and for 60 seconds, thereby obtaining printed fabrics, each of which was a fabric having C ink adhered thereto.

4. Evaluation of Printed Materials 4.1. Rubbing Fastness The rubbing fastness of each of the printed materials obtained by the above-mentioned printing in Examples 1 to 9 and Comparative Examples 1 to 6 was evaluated according to the following evaluation criteria in accordance with the wet test specified in JIS L0849, "Test method for color fastness to rubbing." The test was carried out using the crock meter method. The evaluation was carried out by visually determining the staining grade in accordance with JIS L0801, Clause 10 (Determination of color fastness), which is cited in JIS L0849. The results are shown in Table 3. A rating of C or higher can be said to indicate a good effect.
(Evaluation criteria)
A: The friction resistance exceeds grade 4.
B: The abrasion fastness is at least grade 3-4 (intermediate grade) but not more than grade 4.
C: The abrasion fastness is at least grade 2-3 (intermediate grade) and not more than grade 3.
D: The abrasion fastness is at least grade 1-2 (intermediate grade) but not more than grade 2.
E: The resistance to rubbing is grade 1 or lower.

4.2. Washing Fastness The printed textiles obtained by the above-described textile printing in Examples 1 to 9 and Comparative Examples 1 to 6 were subjected to a washing fastness test in accordance with Method A-2 of JIS L0844 (Testing method for color fastness to washing). Specifically, the printed textiles obtained by the above-described textile printing in Examples 1 to 9 and Comparative Examples 1 to 6 were washed in a household washing machine (ZABOON (trade name), manufactured by Toshiba Corporation) using a general household laundry detergent (fluorescent brightener-free), rinsed, dehydrated, and dried, and then the discoloration of the printed textiles was evaluated. Discoloration was evaluated according to the discoloration gray scale of JIS L0804:2004 (ISO 105-C10(B2)), and the degree of discoloration was evaluated according to the following evaluation criteria. The results are shown in Table 3. A rating of C or higher can be considered to indicate good results.
(Evaluation criteria)
A: Washing fastness is grade 5 or higher.
B: Fastness to washing is grade 4 or higher but lower than grade 5.
C: Fastness to washing is grade 3 or higher but lower than grade 4.
D: Fastness to washing is grade 2 or higher but lower than grade 3.
E: Washing fastness is less than grade 2.

Each of the printed textiles obtained by the above-described textile printing in Examples 1 to 9 and Comparative Examples 1 to 6 was left to stand for 3 days at a room temperature of 25° C. Thereafter, the color density (OD value) of each of the printed textiles after standing to C ink was measured using a fluorescent spectrodensitometer FD-7 (trade name, manufactured by Konica Minolta, Inc.) under the following measurement conditions at a room temperature of 25° C.
(Measurement conditions)
・Observation light source: D65
・Field of view: 2°
・Status: T
- Polarizing filter: Not attached

Thereafter, the OD values for the printed textiles in Examples 1 to 9 and Comparative Examples 2 to 6 were compared with the OD value for the printed textile in Comparative Example 1, and the color development with C ink was evaluated according to the following evaluation criteria. The results are shown in Table 3.
(Evaluation criteria)
A: Compared with the OD value for the printed material in Comparative Example 1, the OD value was 220% or more.
B: Compared with the OD value of the printed material in Comparative Example 1, the OD value was 150% or more and less than 220%.
C: Compared with the OD value of the printed material in Comparative Example 1, the OD value was 100% or more and less than 150%.
D: Compared with the OD value for the printed material in Comparative Example 1, the OD value was 50% or more and less than 100%.
E: Compared with the OD value for the printed material in Comparative Example 1, the OD value was less than 50%.

4.4. Texture The texture of each of the printed textiles obtained by the above-mentioned textile printing in Examples 1 to 13 and Comparative Examples 1 to 5 was evaluated by a sensory test. Specifically, judges performed a sensory evaluation of the feel of the obtained printed textiles and evaluated the texture according to the following criteria. The results are shown in Table 3. Note that even those that received an E rating were durable enough for practical use.
(Evaluation criteria)
A: The printed material is soft and comparable to the original feel of the fabric. B: The printed material is soft, but has a slightly stiff feel.
C: The printed material is slightly hard and feels a little stiff to the touch.
D: The printed material is hard and feels a little stiff to the touch.
E: The printed material is hard and has a significantly stiff feel.

As shown in Table 1, by applying the treatment liquid composition of this embodiment to fabric and then printing the fabric to which the treatment liquid composition has been applied, it has been found that a printed textile can be obtained that has excellent abrasion fastness, washing fastness, and color development, as well as a good texture.

A comparison between Example 1 and Example 2 revealed that printed textiles with superior washing fastness can be obtained when the tertiary amine content is in the range of 1% by mass or more and 3% by mass or less relative to the total amount of the treatment liquid composition.

Comparing Example 2 with Example 4, it was found that using a tertiary amine with a relatively low normal boiling point makes it less likely for the tertiary amine to remain on the printed material, resulting in a printed material with even better rub fastness.

Comparing Example 1 with Example 3, and Example 2 with Example 4, it was found that the use of a tertiary amine having a hydroxyl group resulted in a printed textile with a treatment liquid composition that exhibited superior storage stability.

Comparing Example 8 with Examples 7 and 9, it was found that when the polyester resin content is in the range of 2% by mass or more and 20% by mass or less, calculated as solids content, relative to the total amount of the treatment liquid composition, printed textiles with even better abrasion fastness, washing fastness, and color development can be obtained.

Comparing Example 8 with Examples 7 and 9, it was found that printed textiles with even better abrasion fastness, washing fastness, and color development can be obtained when the combined content of the polyester resin and isocyanate group-containing compound is in the range of 3% by mass or more and 23% by mass or less, calculated as solids content, relative to the total amount of the treatment liquid composition.

A comparison of Example 5 and Example 6 revealed that printed textiles with even better texture can be obtained when the combined content of the polyester resin and the isocyanate group-containing compound is in the range of 3% by mass or more and 10% by mass or less, calculated as solids content, relative to the total amount of the treatment liquid composition.

A comparison of Example 5 and Example 6 revealed that printed textiles with even better texture can be obtained when the content of the isocyanate group-containing compound is in the range of 1% by mass or more and 3% by mass or less, calculated as solids content, relative to the total amount of the treatment liquid composition.

Comparing Examples 1 and 2 with Comparative Examples 5 and 6, it was found that when the mass ratio of tertiary amine to the content of isocyanate group-containing compound is in the range of 0.3 to 5, printed textiles can be obtained that have excellent abrasion fastness, washing fastness, and color development, as well as good texture.

Claims (15)

A treatment liquid composition to be applied to a fabric,
The composition comprises a polyester resin, a tertiary amine, an isocyanate group-containing compound as a crosslinking agent, and water,
A treatment liquid composition for dye textile printing, wherein the content of the tertiary amine is 1% by mass or more and 5% by mass or less based on the total amount of the treatment liquid composition. The dye printing treatment liquid composition according to claim 1, wherein the tertiary amine has a hydroxyl group. The dye printing treatment liquid composition according to claim 1 or 2, wherein the normal boiling point of the tertiary amine is 340°C or lower. The dye printing treatment liquid composition according to any one of claims 1 to 3, wherein the isocyanate group-containing compound has an isocyanurate skeleton in its structure. The dye printing treatment liquid composition according to any one of claims 1 to 4, wherein the content of the polyester resin is 2% by mass or more and 20% by mass or less, calculated as solid content, relative to the total amount of the treatment liquid composition. The dye printing treatment liquid composition according to any one of claims 1 to 5, wherein the content of the isocyanate group-containing compound is 1% by mass or more and 3% by mass or less, calculated as solids content, relative to the total amount of the treatment liquid composition. The dye printing treatment liquid composition according to any one of claims 1 to 6, wherein the total content of the polyester resin and the isocyanate group-containing compound is 3% by mass or more and 23% by mass or less, calculated as solid content, relative to the total amount of the treatment liquid composition. The dye printing treatment liquid composition according to any one of claims 1 to 7, wherein the tertiary amine is one or more selected from the group consisting of triethanolamine, triisopropanolamine, and triethylamine. The dye printing treatment liquid composition according to any one of claims 1 to 8, wherein the mass ratio of the tertiary amine content to the isocyanate group-containing compound content is 0.3 or more and 5 or less. The dye printing treatment liquid composition according to any one of claims 1 to 9, wherein the fabric contains fibers having hydroxyl groups. The dye printing treatment liquid composition according to any one of claims 1 to 10, which is used to adhere to the fabric before dye printing on the fabric. A method for producing a dye textile printing apparatus, comprising: a dye textile printing treatment liquid composition according to any one of claims 1 to 11; and an inkjet ink composition;
The inkjet ink composition comprises a disperse dye and water.
Composition set. A textile printing method comprising a treatment liquid composition application step in which the dye textile printing treatment liquid composition according to any one of claims 1 to 11 is applied to a fabric. a drying step of drying the treatment liquid composition applied to the fabric after the treatment liquid composition application step,
the drying temperature in the drying step is a temperature equal to or higher than the normal boiling point of the tertiary amine contained in the treatment liquid composition;
The textile printing method according to claim 13. a treatment liquid composition applying step of applying the dye textile printing treatment liquid composition provided in the composition set according to claim 12 to a fabric;
a discharge step of discharging the inkjet ink composition provided in the composition set according to claim 12 from a recording head and depositing the ink on an intermediate transfer medium;
a transfer step of transferring the inkjet ink composition adhered to the intermediate transfer medium to the fabric to which the dye textile printing treatment liquid composition has been adhered,
Inkjet printing method.